Functionalisation of CdSe semiconductor nanoparticles with polystyrene brushes by radical polimerization.

CdSe nanoparticles with polystyrene (PS) brushes are obtained by "grafting through" technique starting from solely aqueously synthesized nanoparticles. Mercaptoethanol (ME) capped nanoparticles are used to achieve double bond functional groups on the surface by condensation reaction with methacryloxypropyltrimethoxysilane (MPS). PS polymerization starts from these double bonds. Spectroscopic, diffraction and thermal techniques are used to characterize the nanoparticles. Infrared spectroscopy shows the formation of robust bonding between CdSe nanoparticles and the organic ligand, as well as the presence of the functional double bond on the surface of nanoparticles. Thermal analysis reveals changes in thermal properties of PS, as thermal stability of PS in the functionalised nanoparticles is improved. UV-vis and fluorescence measurements show that PS-CdSe nanoparticles exhibit good optical properties and transmission electron microscope (TEM) micrographs shows good level of dispersion of CdSe nanoparticles in a PS matrix.

Conductive behavior of high TiO2 nanoparticle content of inorganic/organic nanostructured composites.

Amphiphilic polystyrene-b-poly(ethylene oxide) (PS-b-PEO) diblock copolymers with different block ratios were used as templates for the incorporation of a high content of titanium dioxide nanoparticles using the sol-gel method. Confinement of the inorganic part in the PEO block of the block copolymer allows the generation of nanostructured systems with a high nanoparticle content. As successfully demonstrated using tunneling atomic force microscopy, the investigated systems maintained the conductive properties of the TiO(2) nanoparticles. The obtained results confirmed that with increasing TiO(2) nanoparticle content, the local current value increased up to 15 pA, and this conductivity value strongly depended on the amount of the PEO block in the block copolymer template. Moreover, the results indicated that control of the ratio between the sol-gel and the PEO block allows the design of well-dispersed, conductive inorganic/organic hybrids with high inorganic content. These materials can provide attractive strategies in the field of dye-sensitized solar cells.

Surfactant effects on morphology-properties relationships of silver-poly(styrene-b-isoprene-b-styrene) block copolymer nanocomposites.

Good dispersion of silver nanoparticles in poly(styrene-b-isoprene-b-styrene) block copolymer matrix has been achieved by adding dodecanethiol as surfactant to lower the high surface energy of metal nanoparticles. First, the influence of surfactant in the cylindrical nanostructure of neat block copolymer matrix has been analyzed. Taking into account the high solubility between dodecanethiol and the PS block of the SIS block copolymer, when silver nanoparticles and surfactant have been added to the block copolymer matrix its morphology changes from cylindrical to lamellar nanostructure. For the nanocomposite without surfactant, the block copolymer matrix loses its capability to self-assemble in lamellar nanostructure and in this case, agglomeration of silver nanoparticles occurs. Rheological, mechanical and morphological analysis were carried out in order to study the optimal content of surfactant necessary to obtain well-dispersed nanoparticles without worsen the final properties of the nanocomposite. The best silver/dodecanethiol w/w ratio appears to be 1, as confirmed by UV-Vis analysis. Moreover, semi-empirical models, such as Guth and Gold, and Halpin-Tsai, have been used in order to both predict and verify experimental tensile modulus of the obtained nanocomposites. The Guth and Gold equation, applicable to elastomers filled with spherical nanoparticles, provides a result closer to the experimental values than Halpin-Tsai model.

Effect of CdSe nanoparticle addition on nanostructuring of PS-b-P4VP copolymer via solvent vapor exposure.

The surface morphology of poly(styrene-b-4 vinyl pyridine) (PS-b-P4VP) diblock copolymer thin films after solvent vapor annealing has been studied. Morphological features can be switched upon exposure to vapors of a solvent selective for one of the blocks. Self-assembled nanostructures such as hexagonal or striped morphologies were obtained varying vapor exposure time. In addition, the effect of the presence of CdSe nanoparticles located in the P4VP block on obtained nanostructures was analyzed. Atomic force microscopy (AFM) was used for morphological characterization of the block copolymer and the nanocomposites. AFM images showed that nanostructuring was different depending on the amount of CdSe nanoparticles, due to the decrease in P4VP chain mobility.

Bioinspired antimicrobial and biocompatible bacterial cellulose membranes obtained by surface functionalization with aminoalkyl groups.

There has been a great deal of interest in the use of nanostructured bacterial cellulose membranes for biomedical applications, including tissue implants, wound healing, and drug delivery. However, as bacterial cellulose does not intrinsically present antimicrobial properties, in the present study, antimicrobial bacterial cellulose membranes were obtained by chemical grafting of aminoalkyl groups onto the surface of its nanofibrillar network. This approach intends to mimic intrinsic antimicrobial properties of chitosan. Interestingly, these novel grafted bacterial cellulose membranes (BC-NH2) are simultaneously lethal against S. aureus and E. coli and nontoxic to human adipose-derived mesenchymal stem cells (ADSCs) and thus may be useful for biomedical applications. In addition to these biological properties, the bioactive nanostructured BC-NH2 membranes also present improved mechanical and thermal properties.

Optical storage in azobenzene-containing epoxy polymers processed as Langmuir Blodgett films.

In this study, azocopolymers containing different main-chain segments have been synthesized with diglycidyl ether of bisphenol A (DGEBA, DER 332, n=0.03) and the azochromophore Disperse Orange 3 (DO3) cured with two monoamines, viz. benzylamine (BA) and m-toluidine (MT). The photoinduced birefringence was investigated in films produced with these azopolymers using the spin coating (SC) and Langmuir Blodgett (LB) techniques. In the LB films, birefringence increased with the content of azochromophore and the film thickness, as expected. The nanostructured nature of the LB films led to an enhanced birefringence and faster dynamics in the writing process, compared to the SC films. In summary, the combination of azocopolymers and the LB method may allow materials with tuned properties for various optical applications, including in biological systems were photoisomerization may be used to trigger actions such as drug delivery.

Conductive properties of TiO2/bacterial cellulose hybrid fibres.

Conductive properties of TiO(2) nanoparticles and TiO(2)/BC hybrid inorganic/organic fibres were investigated by electrostatic force microscopy (EFM). TiO(2)/BC hybrid composites were prepared based on bacterial cellulose produced by Gluconobacterxylinum, being the bacterial cellulose as a hydrophilic substrate for TiO(2) nanoparticles synthesized via sol-gel. Taken into account hydrophilic nature of the cellulose, TiO(2) nanoparticles were located on the surface of the fibres due to hydrogen bonding interactions. EFM was used to determine qualitatively conductive properties of TiO(2) nanoparticles and their TiO(2)/BC hybrid inorganic/organic fibres. Results indicate that TiO(2)/BC hybrid fibres respond to applied bias regardless of the sign of the applied voltage.

Effect of alkaline and autohydrolysis processes on the purity of obtained hemicelluloses from corn stalks.

A study of the potential of autohydrolysis and alkaline extraction processes from corn stalks was performed for high purity hemicellulose extraction. The influence of process parameters on the purity of obtained hemicelluloses was analyzed. An experimental design was developed for the autohydrolysis treatments to determine the optimal conditions to solubilize the hemicelluloses with lowest content in contaminants. On the other hand, alkaline extraction, including raw material pretreatment (dewaxing and delignification step) was carried out analyzing the effectiveness of this processes for maximum pure hemicellulose recovery. The maximum yield (54% of the raw material hemicelluloses) and the best physicochemical properties (highest hemicellulose content free of lignin) were obtained with these pretreatments in alkaline extraction. Moreover, the effect of lignin removal by sulfuric acid from the autohydrolysis liquors before hemicellulose precipitation was studied. This purification step has allowed to obtain lignin-free autohydrolysis hemicellulose but with the presence of sulfur as predominant contaminant.

Conductive photoswitchable vanadium oxide nanopaper based on bacterial cellulose.

A bacterial cellulose mat was used as a template for the fabrication of conductive photoswitchable hybrid nanopaper by the incorporation of sol-gel synthesized vanadium nanoparticles. The resulting nanopaper, prepared through a green pathway, was able to photoinduce a reversible color change. Conductive properties at the nano- and macroscales were confirmed by electrostatic force microscopy and semiconductor analysis measurements, respectively.

Bacterial cellulose produced by a new acid-resistant strain of Gluconacetobacter genus.

A bacterial strain isolated from the fermentation of Colombian homemade vinegar, Gluconacetobacter medellensis, was investigated as a new source of bacterial cellulose (BC). The BC produced from substrate media consisting of various carbon sources at different pH and incubation times was quantified. Hestrin-Schramm (HS) medium modified with glucose led to the highest BC yields followed by sucrose and fructose. Interestingly, the microorganisms are highly tolerant to low pH: an optimum yield of 4.5 g/L was achieved at pH 3.5, which is generally too low for other bacterial species to function. The cellulose microfibrils produced by the new strain were characterized by scanning and transmission electron microscopy, infrared spectroscopy X-ray diffraction and elemental analysis. The morphological, structural and chemical characteristics of the cellulose produced are similar to those expected for BC.

The role of reactive silicates on the structure/property relationships and cell response evaluation in polyurethane nanocomposites.

Precursors of polyurethane chains have been reacted by means of in situ polymerization with organically modified montmorillonite clay to obtain polyurethane nanocomposites containing from 1 to 4 wt % of nanoreinforcement. The effective final dispersion of inorganic component at nanometric scale was investigated by X-ray diffraction, atomic force microscopy, and transmission electron microscopy. In addition, the effect of the nanoreinforcement incorporation on thermal and mechanical behavior of polyurethane nanocomposites was evaluated. Nanocomposites showed similar mechanical properties to polyurethanes containing high-hard segment contents with higher tensile modulus and a decrease in elastomeric properties of polyurethane materials. Finally, biocompatibility studies using L-929 fibroblast have been carried out to examine in vitro cell response and cytotoxicity of the matrix and their nanocomposite materials. Results suggested that the organic modifier in the clay is unsuitable for biomedical devices in spite of the fact that the matrix is a good candidate for cell adhesion and proliferation.